Addition products from acrylic esters



snprrrom sho pers raom scams as'raas Herman A. Bruson,

hauser,

assignments, to Re delphia, Pa,

R'ydal, and Warren lit. Nieder- Philadelphia, Pa, assignors, by mesne &Haas Company, Philaa corporation of Delaware No'Drawing. ApplicationJune 2i, 1M5, Serial-No. 600,851.

This invention relates to addition products of acrylic acid esters anddryingoil acids or their esters.

- The copolymerization of acrylic esters with drying oils has beendescribed. The products obtained by the hitherto proposed methods areresinous in nature and of large molecular size.

20 Claims. (CE. 260-405) In contrast to such resinous materials, theaddition products of this invention are not polymers or resins. Most ofthe products are distillable under low pressure and are compounds whichare structurally addition products of one moi of acrylic ester per moiof unsaturated fatty acid.

They areprimarily oils.

They are useful as plasticizers and as intermediates for the preparationof dicarboxylic acids" and resins therefrom. They are useful asintermediates for the preparation of amides, including linearpolyarnides.

According to this invention, new products are obtained by reacting byaddition at about 80 C. to about 300 C. esters of acrylic acid andlongchained fatty acids, or esters thereof, in which there are presenttwo oleflnic linkages in conjugate relationship. This addition iseffected in the absence of any polymerizing catalyst and advantageouslyin the presence of an inhibitor for polymerization and/or under an inertatmosphere, such as nitrogen or carbon dioxide.

Typical unsaturated, long-chained, aliphatic or fatty acids having atleast two oleflnic linkages, of which a pair is in conjugaterelationship, are a-elaeostearic acid, fi-elaeostearic acid, a-licanicacid, ,B-licanic acid, and 9,11-octadecadienic acid. Technical mixturesof such acids resulting from hydrolysis of tung oil or oiticica oil maybe used. Likewise, there may be used dehydration products of castor oilor castor oil fatty acids or the acids lcontaining conjugated doublebonds formed by alkaline rearrangement of various unsaturated irate-yacids and esters.

In place of the free fatty acids just described,

there may be reacted the esters of these acids and alcohols, bothmonohydric and polyhydric. An important class of such esters is basedupon monohydric alcohols such as methyl, ethyl, isopropyl, butyl,isobutyl, amyl, 'hexyl, octyl, decyl,

another class of esters is obtained from the unsaturated fatty aoids andpolyhydric alcohols, such as the alkylene glycols, glycerine,pentaerythritol, sorbitol, mannitol, and the like.

' When fatty acid esters of the polyhydric alcohols are reacted with anacrylic acid ester, it is particularly desirable that the reaction beeffected in the presence of a small amount of an inhibitor such ashydroquinone, pyrogallol, naphthylamine, a-naphthol, diphenylamine, orthe like.

Any of the esters of acrylic acid and monohydric alcohols may be used.Typical alcohol groups are methyl, ethyl, isopropyl, butyl, isobutyl,amyl, hexyl, octyl, decyl, dodecyl, cetyl, cyclohexyl, benzyl,chloroethyl, tetrahydrofurfuryl, phenyi, methylphenyl, etc.

Details of the preparation of typical addition products are presented inthe following illustrative examples.

Example 1 A mixture'of 167 parts of tung 011 fatty acids and 77.5 partsof methyl acrylate was heated under reflux for forty-eight hours at95-124 C.

The reaction mixture was distilled under reduced pressure to give 141parts, a 65% yield of addition product, having a boiling range of240-250 C./3 mm. This product was a pale-yellow oil dodecyl, cetyl,stearyl, cyclohexyl, benzyl, chloroethyl, dimethylaminoethyl,phenoxyethyl, tart.- butylphenoxyethyl, tetrahydrofurfuryl, and thelike. The fatty acid esters of moderate molecular weight yield additionproducts with acrylic esters from lower alcohols which are distillable'in high vacuum without decomposition. There may also be used the classof phenyl esters. Yet

having a density, 1120 of 0.9971 and a refractive index, n of 1.4867.The analytical data (saponification number, 301; iodine number, and acidnumber, 150, as compared to the calculated values for Cal-I360. of:Saponiflcation number, 308; iodine number, 140; and acid number of 154)show thatthe distilled product is essentially the adduct of one moi offatty acid and one moi of methyl acrylate.

Example 2 A mixture of 41.7-parts of fi-elaeostearic acid, 17.2 parts ofmethyl acrylate, and 0.2 part of hydroquinone was heated at 1,00fl55 C.under reflux for nineteen hours. Upon vdistillation there wasobtained-35.5 parts (a yield of 65%) of addition product having aboiling range of 240- 244 0/3 mm. The following data were determined forthis product: Saponiflcation number, 306; acid number, iodine number,132; density, d4, 0.9967; and refractive index, 72. 1.4844. I

Example 3 A mixture of 501 parts of tung oil fatty acids, 270 parts ofethyl acrylate, and 0.2 part of hydroquinone was heated at l15-l25 C.under reflux for forty hours. The product was distilled to give underreflux.

Example 4 A mixture of as parts 01 fi-licanic acid, 13 parts of methylacrylate, and 0.2 part or hydroquinone was heated at 90-150 C. fortwenty-seven hours On distillation, there was obtained 29 parts (63%yield) of addition product having a boiling range of 265-275 CJ/4 mm.The product was a thick, pale-yellow oil. The following values weredetermined: Saponiflcation number, 298; density, d4", 1.0427; andrefractive index, n 1.4948. The calculated saponiflcation numher for022113405 is 297.

Example 5 A mixture of 280 parts of octadecadienic acid obtained by thedehydration of ricinoleic acid. 130 parts of ethyl acrylate. and 0.5part of hydroquinone was heated at 115-145 C. under reflux iorsixty-eight hours. The adduct was a paleyellow mm. The following datawere found: Acid number, 135; saponiflcation number, 264; density, d4",0.9505; and refractive index, 11 1.4816.

In place of the methyl and ethyl acrylates used above, other acrylicacid esters may be used with the same sort of addition productresulting.

Example 6 A mixture of 43.8 parts of methyl elaeostearate, 21.5 parts ofmethyl acrylate, and 0.2 part of hydroquinone. was eight hours at 100 to145 C. The reaction mixture was distilled to give 39.5 parts oflight-yellow oil having a boiling range of 220230 C./3 mm., a refractiveindex, o of 1.4775, and a density, (14 of' 0.9762. The analytical data(saponiflcation number, 287, and iodine number, 126, as com- ,pared tothe calculated values for Cali-n04 of: saponification number, 297. andiodine number of 134) show that the product is primarily the adduct ofone moi of methyl acrylate and one moi oi methyl elaeostearate.

Example 7 Example 8 A mixture of 51.5 parts of methyl octadecadienate,obtained by the dehydration of methyl ricinoleate, 26 parts of methylacrylate, and 0.5 partof di-fl-naphthol was placed in an autoclave. Thetemperature of the reaction mixture was gradually raised to 300 C. overa period of one hour. The product was removed and distilled to give 33parts (50% yield) of yellow oil having a boiling range of 235-245 C./4mm., a, density, d4, of 0.9802, and a refractive index, 11 of 1.4736.The saponiflcatlon number determined for this product was 300 incomparison with the theoretical one of 295 for C23H4004.

heated under reflux for forty- In place of the methyl esters of thevariousum.

saturated iatty acids shown above, there may he used any other ester ofthese or other acids having a .pair of conjugated double bonds. Suchester may be that of a polyhydrlc alcohol, as shown in the followingexample.

Emmple 9 A mixture of 291 parts of tung oil, 100 parts-of ethylacrylate, and 2 parts of hydroquinone was heated under reflux fortwenty-one hours at 120- 150 C. to give 390 parts of a. viscous yellowoil.

Two hundred parts of the product was saponiiled by heating under reflux.with stirring, for two hours in 1,000 parts of 25% methanolic sodiumhydroxide. The reaction mixture was acidified to Congo red with 6Nhydrochloric acid and diluted with 2,000 parts of water. The yeloilhaving a boiling range of 235-250 C./4

' separated by low solid was filtered and recrystallized fromnitromethane to give 137 parts (79% yield) of a mixture of isomericdicarboxylic acids. having a melting point of -95 C., and having theformula CIIHZHOA. One of the isomers. which was recrystallization frombutanol, melted at C. Oxidation of this acid with permanganate at 5 C.gave azelaic acid, which demonstrates that the structure of thedicarboxylic acid is 1 We claim: 1. Monomeric addition products of (a)one molecular equivalent of an ester of acrylic acid and a monohydricalcohol and (b) one molecular equivalent of a compound selected from theclass consisting of drying oil fatty acids having conjugate oleflnicbonds and esters thereof.

2. The monomeric addition product of (a) one molecule of an ester ofacrylic acid and a monohydric alcohol and (b) one molecule of a dryingoil fatty acid having conjugate oleflnic bonds.

3. The monomeric addition product from (a) one molecular equivalent 'ofan ester of acrylic acid and a monohydrlc alcohol and (b) one molecularequivalent of an ester of a drying oil fatty acid having conjugateoleflnic bonds.

4. The monomeric addition product of (a) one molecular equivalent of anester of acrylic acid and a monohydric alcohol and (b) one molecularequivalent of an ester of a drying oil fatty acid, having conjugateoleflnic bonds, and asaturated lower aliphatic monohydric alcohol.

5. The monomeric addition product of (a) one molecular equivalent of anester of acrylic acid and a saturated lower aliphatic monohydric alcoholand (b) one molecular equivalent of an ester of a drying oil fatty acid,having conjugate oleflnic bonds, and a saturated lower aliphaticmonohydric alocohol.

6. The monomeric addition product of (a) one molecular equivalent of anester of acrylic acid and a saturated lower aliphatic monohydric alcoholand (bi one molecular equivalent of an ester of elaeostearic acid.

7.. The monomeric addition product of (a) one molecular equivalent of anester of acrylic acid and a saturated lower aliphatic 'monohydricalcohol. and (b) one molecular equivalent of an ester of octadecadienicacid.

8. The monomeric addition product of (a) one molecular equivalent of anester of acrylic acid and a saturated lower aliphatic monohydric alcoholand (b) one molecular equivalent of an ester of elaeostearic acid and asaturated lower aliphatic alcohol.

9. The monomeric addition product of (a) one molecule of an ester ofacrylic acid and a saturated lower aliphatic monohydric alcohol and (b)one molecule of an ester of octadecadienic acid and a saturated loweraliphatic monohydric alcohol.

10. The monomeric addition product of one molecule of ethyl acrylate andone molecule of methyl elaeostearate.

11. The .monomeric addition product of one molecule of ethyl acrylateand one molecule of methyl octadecadienate. p

12. The monomeric addition product of (a) one molecule of an ester ofacrylic acid and a saturated lower aliphatic monohydric alcohol and (b)one molecule of a drying oil fatty acid having conjugate double bonds.

13. The monomeric addition product of one molecule of I ethyl acrylateand one molecule of octadecadienic acid.

14. A method of preparing new monomeric addition products whichcomprises reacting by addition in the absence of polymerization catalystbetween about 80 C. and 300 C. (a) one molecular proportion of an esterof acrylic acid and a monohydric saturated aliphatic alcohol and (b) onemolecular proportion of a compound selected from the class consisting ofdrying oil fatty acids, having conjugate olefinic bonds, and estersthereof.

15. A method of preparing new monomeric addition products whichcomprises reacting by addition in the presence of a polymerizationinhibitor between 80 C. and 300 C. (a) one molecular proportion of anester of acrylic acid and a monohydric saturated aliphatic alcohol and(b) one molecular proportion of a compound selected from the classconsisting of drying oil fatty acids, having conjugate oleflnic bonds,and esters thereof.

16. A method of preparing new monomeric addition products whichcomprises reacting by addition between 80 C. and 300 C. in the absenceof polymerization catalyst and under an inert atmosphere (a) onemolecular proportion of an ester of acrylic acid and a saturated loweraliphatic monohydric alcohol and (b) one addition product whichcomprises reacting by addition between C. and 300 C. in the absence of apolymerization catalyst and under an inert atmosphere (a) one molecularproportion of ethyl acrylate and (b) one molecular proportion of methylelaeostearate.

19. A method of preparing a new monomeric addition product whichcomprises reacting by addition between 80 C. and 300 C. in the absenceof polymerization catalyst and under an inert atmosphere (a) onemolecular proportion of ethyl acrylate and (b) one molecular proportionof methyl octadecadienate.

20. A method of preparing a new monomeric addition product whichcomprises reacting by addition between 80 C. and 300 C. in the absenceof polymerization catalyst and under an inert atmosphere (a) onemolecular proportion of ethyl acrylate and (b) one molecular proportionof octadecadienic acid.

HERMAN A. BRUSON. WARREN D. NIEDERHAUSER.

REFERENCES CITED The following references are of record in the file ofthis patent:

